CN102918003A - Oxide sintered body, target formed from the same, and oxide semiconductor thin film - Google Patents

Oxide sintered body, target formed from the same, and oxide semiconductor thin film Download PDF

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Publication number
CN102918003A
CN102918003A CN2011800256474A CN201180025647A CN102918003A CN 102918003 A CN102918003 A CN 102918003A CN 2011800256474 A CN2011800256474 A CN 2011800256474A CN 201180025647 A CN201180025647 A CN 201180025647A CN 102918003 A CN102918003 A CN 102918003A
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Prior art keywords
film
sintered body
target
oxide semiconductor
oxidate sintered
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CN2011800256474A
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江端一晃
笘井重和
矢野公规
井上一吉
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Publication of CN102918003A publication Critical patent/CN102918003A/en
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    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate
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Abstract

The present invention relates to an oxide sintered body containing oxides of indium and aluminum, and having an atomic ratio Al/(Al + In) of 0.01 to 0.08.

Description

Oxidate sintered body, by its target that forms and oxide semiconductor thin-film
Technical field
The present invention relates to oxidate sintered body, by its target that forms and oxide semiconductor thin-film.
Background technology
The unit electronic component, high-frequency signal amplification element, liquid crystal drive that the electrical effect transistor npn npns such as thin film transistor (TFT) have been widely used as the semiconductor storage unicircuit be with element etc., is the present maximum electron device of practicality.Wherein, follow the remarkable development of display unit in recent years, in the various display unit such as liquid crystal indicator (LCD), el display device (EL), field-emitter display (FED), as apply the switching element that driving voltage drives display unit, multiplex TFT to display element.
Material as the semiconductor layer (channel layer) of the transistorized primary member of field effect mode has been widely used the silicon semiconductor compound most.Usually, used silicon single-crystal at high frequency amplification element that must high speed operation, unicircuit in element etc.On the other hand, liquid crystal drive with element etc. in, for the requirement of big area, used amorphism silicon semiconductor (amorphous silicon).
Although the film of amorphous silicon can form under lower temperature, to compare with crystalline film, switching speed is slow, when therefore using as the switching element that drives display unit, sometimes can not follow the demonstration of animation at a high speed.Particularly, be the LCD TV of VGA for resolution, can use mobility is 0.5～1cm 2The amorphous silicon of/Vs, if but resolution is SXGA, UXGA, QXGA or more than it, then require 2cm 2The mobility that/Vs is above.In addition, if improve driving frequency in order to improve image quality, then need higher mobility.
On the other hand, although crystalline silicon based thin film mobility is high, deposit problem, big area hard problems such as needing during fabrication a large amount of energy and process number.The laser annealing of the equipment of the high temperature when for example, making the silicon based thin film crystallization more than 800 ℃, use high price is necessary.In addition, for crystalline silicon based thin film, owing to consisting of, common element with TFT is defined as the top grid formation, so the costs such as reduction of mask sheet number difficulty.
Usually, the making of oxide semiconductor thin-film is to be undertaken by the sputter of using the target (sputtering target) that is formed by oxidate sintered body.The oxide semiconductor thin-film (patent documentation 1) of adulterated al in Indium sesquioxide for example, is disclosed.Among the embodiment of patent documentation 1, the atomic ratio Al/ (Al+In) that uses indium and aluminium is 0.005 target making oxide semiconductor element.But the research of the tubercle that occurs during about the evaluation of the aspect of performance of target with about sputter is not enough.
The prior art document
Patent documentation
Patent documentation 1: the international brochure that discloses No. 2010/032431
Summary of the invention
The object of the present invention is to provide oxidate sintered body, the paradoxical discharge that it occurs in the time of can suppressing to use sputtering method to form oxide semiconductor thin-film can be stablized and reproducibility obtains oxide semiconductor thin-film well.
The inventor uses the oxidate sintered body Atom that comprises aluminium element, phosphide element and oxygen element than the sputtering target that Al/ (In+Al) is 0.01～0.08, adopts dc sputtering to form oxide semiconductor thin-film.And find that there is following relation in the generation of the paradoxical discharge the when crystalline texture of this target and film forming.That is, find that even perfectly straight stream electric power, also abnormal does not discharge in the situation that the crystallization of the Indium sesquioxide of this target only is comprised of the bixbyite structure basically, if but this crystallization become except the bixbyite structure and also comprise Al 2O 3Deng the state of other structures, paradoxical discharge is multiple.And then find, in the situation that the crystalline texture of oxidate sintered body is comprised of the bixbyite structure, atomic ratio Al/ (In+Al) less than 0.01 situation under, also easily abnormal discharge, the formation tubercle has been finished the present invention.
According to the present invention, provide following oxidate sintered body etc.
1. oxidate sintered body, it contains the oxide compound of indium and aluminium, and atomic ratio Al/ (Al+In) is 0.01～0.08.
2. according to the manufacture method of above-mentioned 1 described oxidate sintered body, comprising: median size is become operation that 0.01～0.08 mode mix modulate mixed powder less than the alumina powder of 1.2 μ m with atomic ratio Al/ (Al+In) less than the indium oxide powder of 1.2 μ m and median size; With above-mentioned mixed powder moulding, make the operation of formed body; With the operation of above-mentioned formed body being burnt till under 1100 ℃～1550 ℃ more than 8 hours.
3. according to the manufacture method of above-mentioned 2 described oxidate sintered bodies, wherein, in oxidizing gas atmosphere, carry out above-mentioned burning till.
4. target of above-mentioned 1 described oxidate sintered body being processed and obtaining.
5. oxide semiconductor thin-film, it is that above-mentioned 4 described targets are carried out sputter, forms film, and said film is annealed and the oxide semiconductor thin-film that obtains, wherein atomic ratio Al/ (Al+In) is 0.01～0.08, has the bixbyite structure of Indium sesquioxide.
6. according to above-mentioned 5 described oxide semiconductor thin-films, wherein, at water partial pressure 5 * 10 -4～7 * 10 -2Carry out above-mentioned sputter under the Pa.
7. thin film transistor, it has above-mentioned 5 or 6 described oxide semiconductor thin-films as channel layer.
8. display unit, it has above-mentioned 7 described thin film transistors.
According to the present invention, oxidate sintered body can be provided, the paradoxical discharge that it occurs in the time of can suppressing to use sputtering method to form oxide semiconductor thin-film can be stablized and reproducibility obtains oxide semiconductor thin-film well.
Description of drawings
Fig. 1 is the figure of the X-ray diffraction measurement result of the sintered compact of manufacturing among the expression embodiment 1.
Fig. 2 is the figure of the X-ray diffraction measurement result of the sintered compact of manufacturing among the expression embodiment 2.
Fig. 3 is the figure of the X-ray diffraction measurement result of the sintered compact of manufacturing among the expression embodiment 3.
Embodiment
Oxidate sintered body of the present invention contains the oxide compound of indium and aluminium, and atomic ratio Al/ (Al+In) is 0.01～0.08.
By making atomic ratio Al/ (Al+In) in above-mentioned scope, become the state of aluminium solid solution in the Indium sesquioxide of bixbyite structure, become low-resistance oxidate sintered body.
Oxidate sintered body of the present invention is low resistance by the solid solution in the Indium sesquioxide of bixbyite structure of aluminium atom, can suppress the generation of paradoxical discharge.
In addition, oxidate sintered body of the present invention owing to comprise the Indium sesquioxide of the bixbyite structure of aluminium atom solid solution, therefore can make the cracking of the target that comprises oxidate sintered body of the present invention and reducing of tubercle.Therefore, oxidate sintered body of the present invention can be efficiently, qurer and energy-conservation form high-quality oxide semiconductor thin-film.
Above-mentioned bixbyite structure can be confirmed by XRD determining.
Oxidate sintered body of the present invention comprises the Indium sesquioxide situation that shows the bixbyite structure can measure by X-ray diffraction (XRD determining) affirmation.
Should illustrate, if X ray incides the crystallization that atomic rule is arranged, observe strong X ray in specific direction, diffraction phenomena occurs.This illustrates by following obtaining: if the path difference of the X ray that is scattered in each position becomes the integral multiple of the wavelength of X ray, then the phase place of ripple is consistent, so wave amplitude becomes large.
Material forms has the separately crystallization of distinctive systematicness, therefore adopts X-ray diffraction can study the kind of compound.In addition, also can carry out the orientation of the crystallization that exists in the size (order of crystallization), material of crystallization distribution (crystalline orientation), put on the evaluation of the residual stress of crystallization.
Oxidate sintered body of the present invention preferably comprises the Indium sesquioxide that shows the bixbyite structure basically, the solid solution in Indium sesquioxide of aluminium atom, and atomic ratio Al/ (Al+In) is 0.01～0.08.
So-called " basically ", mean that effect of the present invention results from above-mentioned bixbyite structure, perhaps 90 volume % of the crystalline texture of oxidate sintered body are above, preferred 95 volume % are above, more preferably 98 volume % are above for showing the Indium sesquioxide crystallization of bixbyite structure.
In addition, oxidate sintered body of the present invention, preferred 90 volume % are above, more preferably 95 volume % are above, further preferred 98 volume % are above is comprised of crystalline texture.Preferably, 90 volume % of oxidate sintered body of the present invention are above to be comprised of crystalline texture, and 90 volume % of this crystalline texture are for showing the Indium sesquioxide of bixbyite structure.
Can calculate volume fraction by the parsing of X-ray diffraction peak.
Be below 0.08 by making atomic ratio Al/ (Al+In), Al is evenly dispersed in the Indium sesquioxide crystallization.On the other hand, atomic ratio Al/ (Al+In) surpasses in 0.08 the situation, and Al does not disperse equably in the bixbyite structure of Indium sesquioxide, might Al 2O 3Deng separating out.If oxidate sintered body contains Al 2O 3Deng other crystalline texture, the target that comprises this oxide crystallization body is carried out in the situation of sputter, might occur easily by paradoxical discharge.
As the reason of above-mentioned paradoxical discharge, be because because target exists unevenly, partly than resistance distinct portions, the impedance that comprises the discharge system of target changes in sputter.This is Al than resistance distinct portions partly 2O 3Deng crystallization, the inhibition that these crystal sizes and number density are reduced for paradoxical discharge is effective.
Atomic ratio Al/ (Al+In) is less than in 0.01 the situation, and the resistance of possible oxidate sintered body rises.If target resistance rises, might occur by paradoxical discharge.
Set out by above viewpoint, the atomic ratio Al/ (Al+In) of the aluminum metal in the oxidate sintered body of the present invention and indium metal is preferably 0.01～0.08, and more preferably 0.01～0.05, more preferably 0.01～0.03.
The atomic ratio of each contained element can be obtained containing element analysis by using inductively coupled plasma apparatus for analyzing luminosity (ICP-AES) in the oxidate sintered body of the present invention.
For example used under the situation of analysis of ICP-AES, it is vaporific with atomizer the solution test portion to be become, import argon plasma (about 6000～8000 ℃), the element absorption heat energy in the test portion and being excited then, orbital electron is moved to the track of high-energy energy level from ground state.This orbital electron is with 10 -7～10 -8Second, degree was moved to the track of more low-yield energy level.This moment with energy difference as light radiation and luminous.This light display is shown the intrinsic wavelength of element (spectral line), therefore can confirm exist (qualitative analysis) of element by having or not of spectral line.In addition, the size of each spectral line (luminous intensity) is proportional with the number of elements in the test portion, therefore compares by the reference liquid with concentration known, can obtain test portion concentration (quantitative analysis).
Like this, determine the element that contains by adopting qualitative analysis, adopt quantitative analysis to obtain content, thereby can obtain the atomic ratio of each element.
The density of oxidate sintered body of the present invention is preferably 6.0g/cm 3More than, 6.3g/cm more preferably 3More than, 6.4g/cm more preferably 3More than.
Density is less than 6.0g/cm 3Situation under, might comprise the surperficial melanism of the sputtering target of oxidate sintered body, bring out paradoxical discharge, sputtering rate descends.The density of oxidate sintered body is particularly preferably 6.3g/cm 3Above 7.1g/cm 3Below.
The maximum particle diameter of the Indium sesquioxide crystallization of the aluminium atom solid solution in the oxidate sintered body is preferably below the 5 μ m.If the particle diameter of Indium sesquioxide crystallization surpasses the growth of 5 μ m ground, might become the reason of tubercle.
Under the situation of sputter with the target surfacing cut, the speed of its cutting is different because of the direction of crystal plane, produces concavo-convex on the target surface.The crystallization particle diameter that this concavo-convex Size-dependent exists in sintered compact for the target that comprises the sintered compact with large crystallization particle diameter, thinks that its concavo-convex change is large, produces tubercle by this convex portion.
The maximum particle diameter of above-mentioned Indium sesquioxide crystallization, being shaped as under the circular situation at the sputtering target that comprises oxidate sintered body of the present invention, at the central point (1 position) of circle with at the center point in 5 positions of total of the intermediate point (4 positions) of the central point on 2 medullary rays of quadrature and circumference, perhaps sputtering target is shaped as in the tetragonal situation, at the center point in 5 positions of total of the intermediate point (4 positions) in the central point on (1 position) and the tetragonal diagonal lines and bight, for its maximum diameter of particle assay of the maximum of in the frame in 100 μ m four directions, observing, the mean value of the particle diameter of the maximum particle that exists separately in the frame at this 5 position.Particle diameter is the major diameter of measuring crystal grain.
Crystal grain can adopt scanning electron microscope (SEM) to observe.
The solid solution in Indium sesquioxide of oxidate sintered body of the present invention, aluminium atom disperses, and the diameter of the aggregate of the aluminium atom of dispersion is preferably less than 1 μ m.By the aluminium atom is slightly disperseed, can carry out stable sputtering discharge.
The diameter of the aggregate of aluminium atom can adopt EPMA (electron beam microanalyzer) to measure.
Film forming speed during d.c. sputtering depends on the ratio resistance of the oxidate sintered body of sputtering target.Therefore, from productive viewpoint, the ratio resistance of preferred oxides sintered compact is low as far as possible, and the ratio resistance of oxidate sintered body of the present invention is preferably below the 0.1 Ω cm, more preferably below the 0.01 Ω cm.Be below the 0.01 Ω cm by making than resistance, can realize faster film forming speed.On the other hand, the ratio resistance of oxidate sintered body surpasses in the situation of 0.1 Ω cm, might adopt the stable film forming difficult of d.c. sputtering.
Should illustrate that the ratio resistance of oxidate sintered body in the manufacturing processed of sintered compact described later, can be processed to reduce by the reduction of heating under the non-oxidizing atmosphere such as nitrogen.
But, if the ratio resistance of oxidate sintered body is below the 0.1 Ω cm, may not carry out stable d.c. sputtering.Even all ratio resistance of oxidate sintered body is below the 0.1 Ω cm, in oxidate sintered body, comprise partly high-resistance material phase (the routine Al described above that has surpassed 0.1 Ω cm 2O 3Equate) situation under, this part is charged by the irradiation of sputter gas ion, so the abnormal discharge, can not stably carry out d.c. sputtering.
Therefore, the part does not contain the high resistance phase, and all ratio resistance of oxidate sintered body is to be important below the 0.1 Ω cm.
Oxidate sintered body of the present invention contains the oxide compound that comprises aluminium element, phosphide element and oxygen element, preferably basically comprises the Indium sesquioxide that shows the bixbyite structure, can contain other inevitable impurity etc. in the scope of not damaging effect of the present invention.
The manufacture method of oxidate sintered body of the present invention comprises: median size is become 0.01～0.08 mode less than the alumina powder of 1.2 μ m with atomic ratio Al/ (Al+In) less than the indium oxide powder of 1.2 μ m and median size mix the operation of modulation mixed powder; The mixed powder moulding is made the operation of formed body; With the operation of formed body being burnt till under 1100 ℃～1550 ℃ more than 8 hours.
Oxidate sintered body of the present invention is not limited by its manufacture method, can be made by the combination of aluminum metal and Indium sesquioxide yet, but preferably use Indium sesquioxide and aluminum oxide as raw material powder.
Have again, as raw material powder, use in the situation of Indium sesquioxide and aluminum metal, the clipped wire that has aluminium in the oxidate sintered body that obtains, in the melting of target surface metal grain, therefore can't emit from target during film forming, the composition of the film that might obtain is different significantly from the composition of oxidate sintered body.
, be preferably below the 1.0 μ m all less than 1.2 μ m as the median size of the indium oxide powder of raw material powder and alumina powder.
The median size of indium oxide powder or alumina powder is under the above situation of 1.2 μ m, and possible aluminium atom is at Indium sesquioxide (In 2O 3) disperse equably in the crystallization.
Should illustrate that the median size of above-mentioned raw materials powder can adopt the mensuration such as laser diffraction formula size-grade distribution device.
With In 2O 3Powder and Al 2O 3Powder becomes 0.01～0.08 mode with atomic ratio Al/ (Al+In) to be mixed.
Be below 0.08 by making atomic ratio Al/ (Al+In), can access the oxidate sintered body that is formed by the Indium sesquioxide that shows the bixbyite structure in fact.
The blending means of raw material powder can adopt wet type or dry ball, vibrating mill, ball mill etc.In order to obtain homogeneous and fine crystal grain and emptying aperture, the crushing efficiency of aggregate dispersion state high, additive also becomes good the ball mill hybrid system most preferably at short notice.
In the situation that ball mill is used for mixing, mixing time was preferably more than 15 hours, more preferably more than 19 hours.This is because if mixing time is not enough, might generate Al in the oxidate sintered body that finally obtains 2O 3Deng the crystalline texture different from the bixbyite structure.
In the situation that ball mill be used for is mixed, mixing time is different because of the amount of slurry of the size of the device that uses and processing, all is below the 1 μ m with the size-grade distribution in the slurry, and the mode that becomes homogeneous is adjusted to suitable.
During the mixing of raw material powder, can add the binding agent of any amount, mix simultaneously.
For above-mentioned binding agent, can use polyvinyl alcohol, vinyl acetate etc.
By hydrous water series solvent in the mixing raw material powder, make the raw material powder slurry, with this raw material powder slurry granulation, with the pelletizing moulding that obtains, can make formed body.
Rapidly drying-granulating is preferably carried out in granulation.As being used for the rapidly device of drying-granulating, be widely used spray-dryer.Concrete drying conditions is by each conditional decisions such as the slurry concentration of the slurry of drying, the hot blast temperature that is used for drying, air quantity.During enforcement, obtain in advance top condition and become necessary.
Should illustrate that for seasoning, because of the difference in specific gravity of raw material powder, settling velocity is different, therefore In might occur 2O 3Powder and Al 2O 3The separation of powder can't obtain the pelletizing of homogeneous.If use this inhomogenous pelletizing to make sintered compact, sometimes at the inner Al that generates of sintered compact 2O 3Deng, become the reason of the paradoxical discharge in the sputter.
The moulding of pelletizing can adopt mold pressing or calm hydraulic pressure pressurization (CIP) to carry out, and the pressure during moulding for example is 1.2 tons/cm 2Above pressure.
The sintering of formed body except normal pressure-sintered method, also can adopt hot pressing, oxygen pressurization, heat respectively to pressure sintering methods such as equipressure pressurizations.
But, from the minimizing of manufacturing cost, mass-produced possibility with can easily make the viewpoint of large-scale sintered compact, preferably adopt normal pressure-sintered method.
For normal pressure-sintered method, with formed body sintering in air atmosphere or oxidizing gas atmosphere, preferably sintering in oxidizing gas atmosphere.
So-called oxidizing gas atmosphere is preferably oxygen atmosphere.It for example is the atmosphere of 10～100 volume % that oxygen atmosphere can be oxygen concn.In the making of oxidate sintered body of the present invention, by in temperature-rise period, importing oxygen atmosphere, can further improve the oxidesintering volume density.
Firing temperature is 1100 ℃～1550 ℃.In addition, firing time is more than 8 hours.
If less than 8 hours, Al is solid solution in the Indium sesquioxide crystallization not, Al less than 1100 ℃ and/or firing time for firing temperature 2O 3Equate to separate out formation in target inside, might become the reason of paradoxical discharge.On the other hand, firing temperature surpasses in 1550 ℃ the situation, because significant grain growing causes the increase of average crystallite particle diameter and the generation of thick emptying aperture, might become the decline of sintered compact intensity, the reason of paradoxical discharge.
Firing temperature is preferably 1200～1550 ℃, more preferably 1250～1500 ℃, is particularly preferably 1300～1450 ℃.
Firing time is preferably 10～50 hours, more preferably 11～40 hours, is particularly preferably 12～30 hours.
Heat-up rate when burning till, preferably making the heat-up rate in 500～1500 ℃ the temperature range is 1～15 ℃/minute.
500～1500 ℃ temperature range is the scope that sintering at utmost carries out.If the heat-up rate of this temperature range is less than 1 ℃/minute, grain growing becomes significantly, might can not realize densification.On the other hand, if heat-up rate surpasses 15 ℃/minute, because the thermal uniformity in the sintering oven reduces, the shrinkage in the possible sintering produces and distributes, the sintered compact fracture.
In the manufacture method of oxidate sintered body of the present invention, for the sintered compact that obtains, also the reduction operation can be set as required.The reduction operation is for volume resistance homogenization in sintered compact is all of the sintered compact that above-mentioned firing process is obtained.
As the method for reducing that can use in the operation in reduction, can enumerate such as the reduction processing of adopting burning till in burning till in the reducing gas, vacuum firing, the rare gas element to carry out etc.
In the situation that the reduction of adopting burning till in the reducing gas to carry out is processed, can use the mixed gas of hydrogen, methane, carbon monoxide or these gas and oxygen etc.
In the situation that the reduction of adopting burning till in the rare gas element to carry out is processed, can use the mixed gas of nitrogen, argon or these gas and oxygen etc.
Temperature when above-mentioned reduction is processed is generally 100～800 ℃, is preferably 200～800 ℃.In addition, the time that reduction is processed is generally 0.01～10 hour, is preferably 0.05～5 hour.
Example as the manufacture method of oxidate sintered body of the present invention is following manufacture method.
Hydrous water series solvent in the raw material powder of the powder mix that contains Indium sesquioxide powder and aluminum oxide powder, mix the slurry that obtains more than 12 hours after, carry out solid-liquid separation, drying and granulation.This granules packed into carry out moulding in framed, the formed body that obtains is burnt till more than 8 hours in oxygen atmosphere, under 1100 ℃～1550 ℃, thereby form oxidate sintered body.
By each condition in the manufacturing process that controls as mentioned above sintered compact, can access sintered density is 6.0g/cm 3More than, than resistance be below the 0.1 Ω cm, the average crystallite particle diameter is below the 10 μ m and only refers to the oxidate sintered body that the bixbyite structure by the Indium sesquioxide of aluminium atom solid solution forms.
By oxidate sintered body of the present invention is processed, can make sputtering target.Particularly, by being the shape that is adapted at installing in the sputter equipment with oxidate sintered body machining of the present invention, can make sputtering target.
The thickness of the target raw material after the machining is generally 2～20mm, is preferably 3～12mm, is particularly preferably 4～6mm.
When making oxidate sintered body become the target raw material, this sintered compact ground with for example plane cut dish and grind and cut, making surface roughness Ra is the following raw materials of 5 μ m.Wherein, further the sputter face of target raw material is implemented mirror finish, can make average surface roughness Ra is below 1000 dusts.This mirror finish (grinding) can adopt mechanical mill, chemical grinding, mechanochemistry to grind known grinding techniques such as (also using of mechanical mill and chemical grinding).For example, can by with the bonded-abrasive polishing machine (polishing liquid: water) be polished down to more than the #2000, perhaps use free abrasive shredder (abrasive substance: SiC stick with paste etc.) to grind after, abrasive substance is replaced by diamond sticks with paste and grind and obtain.There is no particular restriction for such Ginding process.
The preferred ciamond grinder of 200～10,000# that adopts in the surface of target raw material is carried out precision work, particularly preferably adopt the ciamond grinder of 400～5,000# to carry out precision work.If use than 200# little or than 10,000# large ciamond grinder, might rupture easily by the target raw material.
Preferably, the surface roughness Ra of target raw material is below the 0.5 μ m, has the direction-free bevel that grinds.Large or abrasive surface has directivity if Ra is than 0.5 μ m, might the abnormal discharge, perhaps produce particle.
Target raw material after the machining is carried out clean is advisable.For clean, can use air blowing or flowing water washing etc.Adopt to blow when foreign matter removed, from nozzle carry out air-breathingly with suction cleaner towards side, can effectively remove.
Have again, owing to there are the limit in air blowing, flowing water washing, therefore also can further carry out ultrasonic washing etc.The multiple vibration and the method for carrying out is effective between frequency 25～300KHz of this ultrasonic washing.For example between frequency 25～300KHz, interval 25KHz makes 12 kinds of multiple vibrations of frequency and carries out ultrasonic washing and be advisable.
Be combined with backboard by the target raw material that will obtain as mentioned above, can access the sputtering target that is formed by oxidate sintered body of the present invention.In addition, also can be installed on 1 backboard by just a plurality of target raw materials, form in fact 1 target.
The target that comprises oxidate sintered body of the present invention by use carries out film forming, thereby obtains oxide semiconductor thin-film of the present invention.
Above-mentioned film forming can adopt enforcements such as vapour deposition method, sputtering method, ion plating method, pulse laser vapour deposition method.The target that use comprises oxidate sintered body of the present invention adopts the film forming such as sputtering method and the oxide semiconductor thin-film that obtains, because aluminium solid solution in the Indium sesquioxide crystallization, therefore lattice parameter diminishes, and the overlapping change of the 5s track between the indium in the crystallization is large, can expect the raising of mobility.In addition, owing to make the damaged minimizing of oxygen at the Al of In site solid solution, therefore can expect reducing of carrier concentration.
Below following situation is described: the target that comprises oxidate sintered body of the present invention is carried out sputter, forms oxide semiconductor thin-film at substrate.
Oxidate sintered body of the present invention owing to have high conductivity, therefore can be used the fireballing DC sputtering method of film forming.In addition, oxidate sintered body of the present invention except above-mentioned DC sputtering method, also can be used RF sputtering method, AC sputtering method, pulsed D C sputtering method, for any method, all is possible without unusual sputter of discharging.
As sputter gas, can use the mixed gas of argon and oxidizing gas, as oxidizing gas, can enumerate O 2, CO 2, O 3, H 2O etc.
Oxygen partial pressure during spatter film forming is preferably more than 5% below 40%.Oxygen partial pressure less than 5% condition under the film of film forming have electroconductibility, sometimes as the utilization difficulty of oxide semiconductor.Preferably, oxygen partial pressure is more than 10% below 40%.
Substrate temperature during film forming for example is below 500 ℃, is preferably more than 10 ℃ below 400 ℃, more preferably more than 20 ℃ below 350 ℃, is particularly preferably more than 80 ℃ below 300 ℃.
By importing water when the sputter, can prevent from film, producing crystallite.This is because if having crystallite in the film after accumulation at once, and therefore 2 crystallizations by annealing become the many films of defective, might cause the rising of carrier concentration, the decline of mobility.
Water partial pressure during spatter film forming is preferably 5 * 10 -4～7 * 10 -2Pa.Water partial pressure is less than 5 * 10 -4In the situation of Pa, might behind film stack, namely be engraved in and generate crystallite in the film.On the other hand, water partial pressure surpasses 7 * 10 -2In the situation of Pa, because the decline of film density becomes significantly, therefore might diminish by the overlapping of In5s track, cause the decline of mobility.
By the film on the substrate that adopts spatter film forming is carried out anneal, thin film crystallization obtains characteristic of semiconductor.In addition, oxide semiconductor thin-film of the present invention is by implementing anneal, Al solid solution in the Indium sesquioxide crystallization, the single-phase of demonstration bixbyite.
The anneal temperature for example is below 500 ℃, is preferably more than 100 ℃ below 500 ℃, more preferably more than 150 ℃ below 400 ℃, is particularly preferably more than 200 ℃ below 350 ℃.
During to film forming and the heating atmosphere during anneal be not particularly limited, from the controlled viewpoint of current carrier, preferred atmosphere atmosphere or oxygen flow ventilation atmosphere.
In the anneal, can use lamp annealing device, laser apparatus annealing device, thermal plasma body device, hot air heating apparatus, Contact Heating device etc. in the presence of oxygen or not.
The oxide semiconductor thin-film of the present invention that obtains like this contains the oxide compound of indium and aluminium, atomic ratio Al/ (Al+In) in this film is 0.01～0.08, preferably formed by the Indium sesquioxide that shows the bixbyite structure in fact, aluminium solid solution in Indium sesquioxide, the atomic ratio Al/ (Al+In) in this film is 0.01～0.08.
The value that the atomic ratio Al/ (Al+In) of the target (sintered compact) that uses in atomic ratio Al/ (Al+In) demonstration of film and the film forming of this film is same should be described.
Oxide semiconductor thin-film of the present invention can be used in thin film transistor, is particularly suitable for the channel layer of thin film transistor.
Have oxide semiconductor thin-film of the present invention and can be the channel-etch type as the thin film transistor of channel layer (below be sometimes referred to as thin film transistor of the present invention).Therefore oxide semiconductor thin-film of the present invention is crystalline film, has weather resistance, and in the manufacturing of thin film transistor of the present invention, the photo-mask process that the metallic film etching of Mo etc. is formed source-drain electrode, groove also becomes possibility.
Thin film transistor of the present invention also can be the etch stopper type.Oxide semiconductor thin-film of the present invention, etch stopper can be protected the groove that is formed by semiconductor layer, and makes a large amount of oxygen enter semiconductor layer during film forming, so that become unnecessary via etch stopper from the outside for oxygen supply.In addition, it is possible at once making amorphous membrance after the film forming, when the metallic film etching of Mo etc. is formed source-drain electrode, groove, can the etching semiconductor layer, and shorten photo-mask process and also become possibility.
Embodiment
[manufacturing of oxidate sintered body and target]
Embodiment 1-3
The aluminum oxide powder of the equal particle diameter 0.97 μ m of Indium sesquioxide powder peace of weighing median size 0.98 μ m, adds moulding and carries out granulation with binding agent after Crushing of Ultrafine mixes equably to become the atomic ratio Al/ (Al+In) shown in the table 1.Next, this raw material powder mix is filled in the mould equably, under moulding pressure 140MPa, carries out extrusion forming with chilling press.The formed body that obtains is like this burnt till under the firing temperature shown in the table 1 and firing time with sintering oven, make sintered compact.
Firing atmosphere is oxygen atmosphere in intensification, is (atmosphere) in the atmosphere in addition, burns till with 1 ℃/minute of heat-up rate, 15 ℃ of/minute enforcements of cooling rate.
Should illustrate that the median size of the raw material oxide powder of use adopts laser diffraction formula particle size distribution device SALD-300V (Shimadzu Seisakusho Ltd.'s system) to measure, median size adopts intermediate value footpath D50.
For the sintered compact that obtains, the X ray picture that uses X-ray diffraction determinator (リ ガ Network Ultima-III processed) that crystalline texture is investigated the sintered compact of embodiment 1-3 is shown in Fig. 1-3.
Figure is analyzed, and the result only observes the bixbyite structure of Indium sesquioxide in the sintered compact of embodiment 1-3.This crystalline texture can be confirmed by enough JCPDS (Joint Committee of PowderDiffraction Standards) card.The bixbyite structure of Indium sesquioxide is JCPDS card No.06-0416.
The condition determination of above-mentioned X-ray diffraction mensuration (XRD) is as described below.
Device: (strain) リ ガ Network Ultima-III processed
X ray: Cu-K α line (wavelength
Figure BDA00002455441800131
Use the graphite monochromator monochromatization)
2 θ-θ reflection method, continuous sweep (1.0 °/minutes)
Sampling interval: 0.02 °
Slit DS, SS:2/3 °, RS:0.6mm
Weight and a profile cun method by the sintered compact that is cut into a certain size are calculated the density of the sintered compact that obtains.In addition, use resistrivity meter (Mitsubishi Chemical's (strain) system, ロ レ ス タ) to measure the volume resistance (electroconductibility) of the sintered compact that obtains based on four probe method (JIS R 1637).Show the result in table 1.
For the sintered compact that obtains, measure to investigate the dispersion of Al by EPMA.Its result does not observe the aggregate of the above aluminium atom of 1 μ m, and the dispersiveness of the sintered compact of embodiment 1-3, homogeneity are extremely excellent as can be known.
The condition determination of EPMA is as described below.
Device name: JXA-8200 (Jeol Ltd.'s system)
Acceleration voltage: 15kV
Irradiation electric current: 50nA
Irradiation time (per 1 point): 50mS
Grind with the plane and to cut dish and grind the surface of cutting the oxidate sintered body that obtains among the embodiment 1-3, side is cut off with the diamond cutting cutter, be pasted on backboard, make respectively 4 inches
Figure BDA00002455441800132
Sputtering target.
The sputtering target that obtains is installed on the DC sputter equipment, use argon gas as sputter gas, press 0.4Pa, substrate temperature with sputter: room temperature, DC power 400W carry out the continuous sputter of 10kWh, and the variation of voltage in the sputter is accumulated in data recorder, confirm having or not of paradoxical discharge.Show the result in table 1.
Should illustrate that having or not by the monitoring voltage change of above-mentioned paradoxical discharge detects paradoxical discharge and carry out.Particularly, be that the situation more than 10% of the permanent voltage in the sputter running is as paradoxical discharge with the variation of voltage that occurs in 5 minutes the minute.Particularly the permanent voltage in the sputter running is under the situation of change ± 10% in 0.1 second, occurs as little electric arc of the paradoxical discharge of sputtering discharge, and the yield of element descends, and might be not suitable for a large amount of productions.
In addition, use the sputtering target of embodiment 1-3, use the mixed gas that in argon gas, has added 3% hydrogen as atmosphere, carried out sputter, and confirmed to have inarticulate generation in continuous 30 hours.Its result does not observe tubercle on the sputtering target surface of embodiment 1-3.
Should illustrate that sputtering condition is that 0.4Pa, DC power 100W, substrate temperature are pressed in sputter: room temperature, the hydrogen that adds is used for promoting the generation of tubercle in atmosphere gas.
For tubercle, adopt following method: the variation on the target surface after adopting stereomicroscope with sputter is amplified to 50 times and observes, for visual field 3mm 2The tubercle that 20 μ m of middle generation are above, the instrumentation number is average.The tubercle number that occurs is shown in table 1.
[table 1]
Figure BDA00002455441800141
Comparative example 1-3
Except the aluminum oxide powder of the equal particle diameter 0.97 μ m of Indium sesquioxide powder peace of weighing median size 0.98 μ m to become the atomic ratio Al/ (Al+In) shown in the table 2, beyond burning till with the firing temperature shown in the table 2 and firing time, similarly make sintered compact and target with embodiment 1-3, estimate.Show the result in table 2.
Should illustrate that 1 of comparative example is made sintered compact and target with the Indium sesquioxide powder.
Comparative example 4 and 5
Except replacing aluminum oxide, the yttrium oxide powder (Y of weighing median size 1.06 μ m in comparative example 4 2O 3Powder), the boron oxide powder (B of weighing median size 1.02 μ m in comparative example 5 2O 3Powder) to become the atomic ratio M (M+In) shown in the table 2, beyond burning till with the firing temperature shown in the table 2 and firing time, similarly makes sintered compact and target with embodiment 1-3, estimate.Show the result in table 2.
[table 2]
Figure BDA00002455441800151
As shown in Table 2, used in the situation of sputtering target of comparative example 1-5, paradoxical discharge occurs in sputter, and observes tubercle on the target surface.In addition, for the use of comparative example 4 and 5 sintered compact of yttrium oxide and boron oxide, with the target of embodiment 1-3 relatively, sintered density is low significantly as can be known.
For the sintered compact of comparative example 1-5, similarly adopt the X-ray diffraction determinator to investigate crystalline texture with embodiment 1-3.Its result for the sintered compact of comparative example 3, in X-ray diffractogram, except the bixbyite structure, also observes the Al with corundum structure 2O 3Phase.This crystalline texture can be confirmed by enough JCPDS cards.If Al 2O 3The corundum structure, can be enough card JCPDS No.10-173 confirm.
[film forming of oxide semiconductor thin-film and the manufacturing of thin film transistor]
Embodiment 4
On glass substrate and with the heat oxide film (SiO of thick 100nm 2) silicon substrate on use respectively the target (Al/ (In+Al)=0.013) that obtains among the embodiment 1, adopt the DC magnetron sputtering system to form the film of thickness 50nm.
Sputter is to carry out vacuum exhaust until back pressure reaches 1 * 10 -4Behind the Pa, the limit makes argon gas 9.9sccm, water 0.1sccm (water partial pressure: 4.0 * 10 -3Pa) flow into, the limit is adjusted to 0.4Pa with pressure, at room temperature carries out with sputtering power 100W.
Crystalline texture on the employing XRD affirmation glass substrate after the firm film forming of the film of film forming.Its result does not observe clearly diffraction peak, confirms as amorphous.The glass substrate that has formed this film is dropped in the process furnace that is heated to 300 ℃ in the air, carry out processing in 1 hour.For the film after the anneal, carry out XRD determining, the result only observes the peak of the bixbyite structure of Indium sesquioxide.This crystalline texture can be confirmed by enough JCPDS card No.06-0416.
In addition, by Hall effect mensuration carrier concentration and the mobility of the film after the anneal are estimated, carrier concentration is 6.98 * 10 as a result 17Cm -3, hall mobility is 24.5cm 2/ Vs.The atomic ratio of also confirming the film after the anneal is identical with the atomic ratio of the target of use.
At the silicon substrate that has formed film (electroconductibility silicon substrate) metal mask is set, forms the groove of L:200 μ m, W:1000 μ m, gold evaporation has formed source-drain electrode.This element is dropped in the process furnace that is heated to 300 ℃, carry out processing in 1 hour, thereby make thin film transistor.
For the thin film transistor of making, electrical effect mobility, on-off ratio and S value are estimated.Its result, electrical effect mobility are 38.8cm 2/ Vs, the on-off ratio is 8.18 * 10 8, showing normal characteristic of closing, the S value confirms as 0.66.
Embodiment 5
On glass substrate and with the heat oxide film (SiO of thick 100nm 2) silicon substrate on, use respectively the target (Al/ (In+Al)=0.027) that obtains among the embodiment 2 to adopt the DC magnetron sputtering system to form the film of thickness 50nm.
Sputter is to carry out vacuum exhaust until back pressure reaches 1 * 10 -4Behind the Pa, the limit makes argon gas 9.9sccm, water 0.1sccm (water partial pressure: 4.0 * 10 -3Pa) flow into, the limit is adjusted to 0.4Pa with pressure, at room temperature carries out under sputtering power 100W.
Adopt the crystalline texture of XRD affirmation after the firm film forming of the film of film forming on the glass substrate.Its result does not observe clearly diffraction peak, confirms as amorphous.The glass substrate that has formed this film is dropped in the process furnace that is heated to 300 ℃ in the air, carried out processing in 1 hour.Carried out XRD determining for the film after the anneal, the result only observes the peak of the bixbyite structure of Indium sesquioxide.This crystalline texture can be confirmed by enough JCPDS card No.06-0416.
In addition, by Hall effect mensuration carrier concentration and the mobility of the film after the anneal are estimated, carrier concentration is 2.37 * 10 as a result 17Cm -3, hall mobility is 22.1cm 2/ Vs.
At the silicon substrate that has formed film (electroconductibility silicon substrate) metal mask is set, forms the groove of L:200 μ m, W:1000 μ m, gold evaporation has formed source-drain electrode.This element is dropped in the process furnace that is heated to 300 ℃, carry out processing in 1 hour, thereby make thin film transistor.
For the thin film transistor of making, electrical effect mobility, on-off ratio and S value are estimated.Its result, electrical effect mobility are 31.1cm 2/ Vs, the on-off ratio is 3.11 * 10 8, showing normal characteristic of closing, the S value confirms as 0.52.
Embodiment 6
On glass substrate and with the heat oxide film (SiO of thick 100nm 2) silicon substrate on, use respectively the target (Al/ (In+Al)=0.078) that obtains among the embodiment 3 to adopt the DC magnetron sputtering system to form the film of thickness 50nm.
Sputter is to carry out vacuum exhaust until back pressure reaches 1 * 10 -4Behind the Pa, the limit makes argon gas 9.9sccm, water 0.1sccm (water partial pressure: 4.0 * 10 -3Pa) flow into, the limit is adjusted to 0.4Pa with pressure, at room temperature carries out under sputtering power 100W.
Adopt the crystalline texture of XRD affirmation after the firm film forming of the film of film forming on the glass substrate.Its result does not observe clearly diffraction peak, confirms as amorphous.The glass substrate that has formed this film is dropped in the process furnace that is heated to 300 ℃ in the air, carried out processing in 1 hour.Carried out XRD determining for the film after the anneal, the result only observes the peak of the bixbyite structure of Indium sesquioxide.This crystalline texture can be confirmed by enough JCPDS card No.06-0416.
In addition, by Hall effect mensuration carrier concentration and the mobility of the film after the anneal are estimated, carrier concentration is 5.88 * 10 as a result 16Cm -3, hall mobility is 18.8cm 2/ Vs.
At the silicon substrate that has formed film (electroconductibility silicon substrate) metal mask is set, forms the groove of L:200 μ m, W:1000 μ m, gold evaporation has formed source-drain electrode.This element is dropped in the process furnace that is heated to 300 ℃, carry out processing in 1 hour, thereby make thin film transistor.
For the thin film transistor of making, electrical effect mobility, on-off ratio and S value are estimated.Its result, electrical effect mobility are 24.3cm 2/ Vs, the on-off ratio is 2.56 * 10 8, showing normal characteristic of closing, the S value confirms as 0.77.
Comparative example 6
On glass substrate and with the heat oxide film (SiO of thick 100nm 2) silicon substrate on, the target that obtains in the usage comparison example 3 respectively (Al/ (In+Al)=0.23) adopts the DC magnetron sputtering system to form the film of thickness 50nm.
Sputter is to carry out vacuum exhaust until back pressure reaches 1 * 10 -4Behind the Pa, the limit makes argon gas 9.9sccm, water 0.1sccm (water partial pressure: 4.0 * 10 -3Pa) flow into, the limit is adjusted to 0.4Pa with pressure, at room temperature carries out under sputtering power 100W.
Adopt the crystalline texture of XRD affirmation after the firm film forming of the film of film forming on the glass substrate.Its result does not observe clearly diffraction peak, confirms as amorphous.The glass substrate that has formed this film is dropped in the process furnace that is heated to 300 ℃ in the air, carried out processing in 1 hour.Carried out XRD determining for the film after the anneal, the result does not observe clearly diffraction peak, confirms as amorphous.
In addition, by Hall effect mensuration carrier concentration and the mobility of the film after the anneal are estimated, carrier concentration is 7.28 * 10 as a result 16Cm -3, hall mobility is 9.7cm 2/ Vs, to compare hall mobility poor significantly with the film of embodiment 4～6 as can be known.
At the silicon substrate that has formed film (electroconductibility silicon substrate) metal mask is set, forms the groove of L:200 μ m, W:1000 μ m, gold evaporation has formed source-drain electrode.This element is dropped in the process furnace that is heated to 300 ℃, carry out processing in 1 hour, thereby make thin film transistor.
For the thin film transistor of making, electrical effect mobility, on-off ratio and S value are estimated.Its results verification, electrical effect mobility are 7.8cm 2/ Vs, the on-off ratio is 2.43 * 10 6, showing normal characteristic of closing, the S value is 1.87.Compare with the transistor of embodiment 4～6, as can be known electrical effect migration rate variance.
Utilize possibility on the industry
The sputtering target that comprises oxidate sintered body of the present invention can be used in the manufacturing of thin film transistor etc.In addition, thin film transistor of the present invention can be used in unicircuit etc.
Above-mentioned several embodiments of the present invention and/or embodiment are had been described in detail, but those skilled in the art are in the situation that does not basically break away from new instruction of the present invention and effect, and it is easy introducing a large amount of distortion in these illustrative embodiments and/or embodiment.Therefore, these a large amount of distortion within the scope of the present invention.
The content of the document put down in writing in this specification sheets all is applied at this paper.

Claims (8)

1. an oxide sintered body, it contains the oxide compound of indium and aluminium, and atomic ratio Al/ (Al+In) is 0.01～0.08.
2. the manufacture method of an oxidate sintered body claimed in claim 1, it comprises:
Median size is mixed to modulate mixed powder less than indium oxide powder and the median size of 1.2 μ m as 0.01～0.08 mode take atomic ratio Al/ (Al+In) less than the alumina powder of 1.2 μ m operation;
Described mixed powder moulding is made the operation of formed body; And
Under 1100 ℃～1550 ℃, described formed body burnt till the operation more than 8 hours.
3. the manufacture method of oxidate sintered body according to claim 2 wherein, is carried out described burning till in oxidizing gas atmosphere.
4. target, it is processed oxidate sintered body claimed in claim 1 and obtains.
5. oxide semiconductor thin-film, it is to form film by target claimed in claim 4 being carried out sputter, and described film is annealed and the oxide semiconductor thin-film that obtains,
Wherein atomic ratio Al/ (Al+In) is 0.01～0.08, and has the bixbyite structure of Indium sesquioxide.
6. oxide semiconductor thin-film according to claim 5, wherein, at water partial pressure 5 * 10 -4～7 * 10 -2Carry out described sputter under the Pa.
7. thin film transistor, it has claim 5 or 6 described oxide semiconductor thin-films as channel layer.
8. display unit, it has thin film transistor claimed in claim 7.
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